Laundry detergent compositions with certain cationically charged dye maintenance polymers

ABSTRACT

The present invention relates to laundry detergent compositions providing dye protection benefits to fabric comprising: a) from about 4% to about 70% by weight, of a surfactant; b) from about 0.01% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more linearly polymerizing monomers, cyclically polymerizing monomers, and mixtures thereof; and c) the balance carriers and adjunct ingredients.

This application claims priority to PCT application no. PCT/US00/08031,filed Mar. 24, 2000, and U.S. provisional application No. 60/126,072,filed Mar. 25, 1999.

FIELD OF THE INVENTION

The present invention relates to compositions, in either liquid orgranular form, for use in laundry applications, wherein the compositionscomprise certain dye maintenance polymers that have a net positivecharge. Compositions comprising the dye maintenance polymers of thisinvention impart appearance and integrity benefits to fabrics andtextiles laundered in washing solutions formed from such compositions.

BACKGROUND OF THE INVENTION

It is, of course, well known that alternating cycles of using andlaundering fabrics and textiles, such as articles of worn clothing andapparel, will inevitably adversely affect the appearance and integrityof the fabric and textile items so used and laundered. Fabrics andtextiles simply wear out over time and with use. Laundering of fabricsand textiles is necessary to remove soils and stains which accumulatetherein and thereon during ordinary use. However, the launderingoperation itself, over many cycles, can accentuate and contribute to thedeterioration of the integrity and the appearance of such fabrics andtextiles.

Deterioration of fabric integrity and appearance can manifest itself inseveral ways. Short fibers are dislodged from woven and knitfabric/textile structures by the mechanical action of laundering. Thesedislodged fibers may form lint, fuzz or “pills” which are visible on thesurface of fabrics and diminish the appearance of newness of the fabric.Further, repeated laundering of fabrics and textiles, especially withbleach-containing laundry products, can remove dye from fabrics andtextiles and impart a faded, worn out appearance as a result ofdiminished color intensity, and in many cases, as a result of changes inhues or shades of color.

Given the foregoing, there is clearly an ongoing need to identifymaterials which could be added to laundry products that would associatethemselves with the fibers of the fabrics and textiles laundered usingsuch products and thereby reduce or minimize the tendency of thelaundered fabric/textiles to deteriorate in appearance. Any suchdetergent product additive material should, of course, be able tobenefit fabric appearance and integrity without unduly interfering withthe ability of the laundry product to perform its intended function. Thepresent invention is directed to the use of dye maintenance polymers inlaundry applications that perform in this desired manner.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned need in that it has beensurprisingly discovered that fabric which is treated, and subsequentlyre-treated with the compositions of the present invention, will resistnormal fading and color loss without regard to the circumstances, interalia, due to mechanical wear and abrasion. In addition, fabric which hasnot been treated can have the loss of fabric dye attenuated by washingclothing with the laundry detergent compositions of the presentinvention. The compositions of the present invention can take any form,inter alia, heavy duty liquid (HDL), heavy duty granular (HDG), bars,pastes, thixotropic compositions.

The first aspect of the present invention relates to laundry detergentcompositions providing dye protection benefits to fabric comprising:

a) from about 4% to about 70% by weight, of a surfactant selected fromthe group consisting of nonionic, anionic, cationic, amphoteric,zwitterionic surfactants and mixtures thereof, preferably at least oneof said surfactants is an anionic surfactant;

b) from about 0.01%, preferably from about 0.1%, more preferably fromabout 0.5%, most preferably from about 0.8% to about 10%, preferably toabout 8%, more preferably to about 6%, most preferably to about 5% byweight, of a dye maintenance polymer or oligomer, said polymer orcopolymer comprising one or more units having the formula:

I) linear polymer units having the formula:

 wherein each R¹ is independently

a) hydrogen;

b) C₁-C₄ alkyl;

c) substituted or unsubstituted phenyl;

d) substituted or unsubstituted benzyl;

e) carbocyclic;

f) heterocyclic;

g) and mixtures thereof;

each R² is independently

a) hydrogen;

b) halogen

c) C₁-C₄ alkyl;

d) C₁-C₄ alkoxy;

e) substituted or unsubstituted phenyl;

f) substituted or unsubstituted benzyl;

g) carbocyclic;

h) heterocyclic;

i) and mixtures thereof;

each Z is independently

a) hydrogen;

b) hydroxyl;

c) halogen;

d) —(CH₂)_(m)R;

wherein R is:

i) hydrogen;

ii) hydroxyl

iii) halogen;

iv) nitrilo;

v) —OR³;

vi) —O(CH₂)_(n)N(R³)₂;

vii) —O(CH₂)_(n)N⁺(R³)₃X⁻;

viii) —OCO(CH₂)_(n)N(R³)₂;

ix) —OCO(CH₂)_(n)N⁺(R³)₃X⁻;

x) —NHCO(CH₂)_(n)N(R³)₂;

xi) —NHCO(CH₂)_(n)N⁺(R³)₃X⁻;

xii) —(CH₂)_(n)N(R³)₂;

xiii) —(CH₂)_(n)N⁺(R³)₃X⁻;

xiv) carbocyclic;

xv) heterocyclic;

xvi) nitrogen heterocycle quaternary ammonium;

xvii) nitrogen heterocycle N-oxide;

xviii) aromatic N-heterocyclic quaternary ammonium;

xix) aromatic N-heterocyclic N-oxide;

xx) —NHCHO;

xxi) or mixtures thereof;

each R³ is independently hydrogen, C₁-C₈ alkyl, C₂-C₈ hydroxyalkyl, andmixtures thereof; X is a water soluble anion; the index n is from 0 to 6

e) —(CH₂)_(m)COR′

wherein R′ is

i) —OR³;

ii) —O(CH₂)_(n)N(R³)₂;

iii) —O(CH₂)_(n)N⁺(R³)₃X⁻;

iv) —NR³(CH₂)_(n)N(R³)₂;

v) —NR³(CH₂)_(n)N⁺(R³)₃X⁻;

vi) —(CH₂)_(n)N(R³)₂;

vii) —(CH₂)_(n)N⁺(R³)₃X⁻;

viii) or mixtures thereof;

each R³ is independently hydrogen, C₁-C₈ alkyl, C₂-C₈ hydroxyalkyl, andmixtures thereof; X is a water soluble anion; the index n is from 0 to6;

f) and mixtures thereof; the index m is from 0 to 6;

II) cyclic units derived from cyclically polymerizing monomers havingthe formula:

 wherein each R⁴ is independently an olefin comprising unit which iscapable of propagating polymerization in addition to forming a cyclicresidue with an adjacent R⁴ unit; R⁵ is C₁-C₁₂ linear or branched alkyl,benzyl, substituted benzyl, and mixtures thereof; X is a water solubleanion; and

III) mixtures thereof; provided said polymer or co-polymer has a netcationic charge; and wherein said dye maintenance polymer is not anpolyethyleneimine or alkoxylated derivative thereof; and

b) the balance carriers and other adjunct ingredients.

In addition to the surfactant and the dye maintenance polymer of thisinvention, the laundry detergent compositions herein comprise from about0.01% to 80% by weight of an organic or inorganic detergency builder andother conventional laundry detergent products. In its method aspect, thepresent invention relates to the laundering or treating of fabrics andtextiles in aqueous washing, rinsing, or treating solutions formed fromeffective amounts of any of the detergent compositions, fabric softenercompositions, or aqueous solution treatments described herein, or formedfrom the individual components of such compositions. Laundering offabrics and textiles in such washing, rinsing and/or treatmentsolutions, followed by drying, imparts fabric appearance benefits to thefabric and textile articles so treated. Such benefits can includeimproved overall appearance, pill/fuzz reduction, anti-fading, improvedabrasion resistance, and/or enhanced softness. It has been surprisinglydetermined that the dye maintenance polymers of this invention impartfabric appearance and integrity benefits that are greater than thebenefits achieved by a corresponding amount of either component byitself.

These and other objects, features and advantages will become apparent tothose of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight, unless otherwise specified. Alltemperatures are in degrees Celsius (°C.) unless otherwise specified.All documents cited are in relevant part, incorporated herein byreference.

DETAILED DESCRIPTION OF THE INVENTION

As noted, when fabric or textiles are laundered in solutions whichcomprise the dye maintenance polymers of the present invention fabricappearance and integrity are enhanced. The dye maintenance polymers canbe added to wash solutions by incorporating them into a detergentcomposition, a fabric softener or by adding them separately to thewashing solution. The dye maintenance polymers are described hereinprimarily as liquid or granular detergent additives but the presentinvention is not meant to be so limited. The dye maintenance polymers,detergent composition components, optional ingredients for suchcompositions and methods of using such compositions, are described indetail below. All percentages are by weight unless other specified.

Dye Maintenance Polymers

Compositions and systems of the present invention comprise from about0.1%, preferably for about 1%, more preferably from about 2%, mostpreferably from about 3% to about 10%, preferably to about 7%, morepreferably to about 5% by weight, of a polymer, co-polymer, or mixturethereof, wherein said polymer or co-polymer comprises at least onecationically charged unit, inter alia, quaternary ammonium moiety orunit which can form a cationic charge in situ, inter alia, primary aminemoiety. Stated in another way, the oligomer, polymer, or co-polymerresulting from the herein below described monomer units must have a netcationic charge. The charge can be distributed among any of the hereindescribed units.

The dye maintenance polymers of this invention can be used in any fabriclaundering process and provide certain appearance benefits to thefabrics laundered in these processes. Such fabric appearance benefitscan include, for example, improved overall appearance of the launderedfabrics, reduction of the formation of pills and fuzz, protectionagainst color fading, improved abrasion resistance, etc. The dyemaintenance polymers used in the compositions and methods herein canprovide such fabric appearance benefits when incorporated in a wash orrinse added products.

As will be apparent to those skilled in the art, an oligomer is amolecule consisting of only a few monomer units while polymers compriseconsiderably more monomer units. For the present invention, oligomersare defined as molecules having an average molecular weight below about1,000 and polymers are molecules having an average molecular weight ofgreater than about 1,000. Copolymers are polymers or oligomers whereintwo or more dissimilar monomers have been simultaneously or sequentiallypolymerized. Copolymers of the present invention can include, forexample, polymers or oligomers copolymerizing acrylamide withdimethyldiallylammonium chloride, vinyl amine with vinyl alcohol, etc

Cationic polymers in general and their method of manufacture are know.For example, a detailed description of cationic polymers can be found inan article by M. Fred Hoover that was published in the Journal ofMacromolecular Science—Chemistry, A4(6), pp 1327-1417, October, 1970.The entire disclosure of the Hoover article is incorporated herein byreference. The dye maintenance polymers of this invention will be betterunderstood when read in light of the Hoover article, the presentdisclosure and the Examples herein.

I) Linear Polymer Units

The polymers or co-polymers of the present invention can comprise one ormore linear polymer units having the formula:

wherein R¹, R², and Z are defined herein below. Preferably, the linearpolymer units are formed from linearly polymerizing monomers. Linearlypolymerizing monomers are defined herein as monomers which understandard polymerizing conditions result in a linear polymer chain oralternatively which linearly propagate polymerization. The linearlypolymerizing monomers of the present invention have the formula:

however, those of skill in the art recognize that many useful linearmonomer units are introduced indirectly, inter alia, vinyl amine units,vinyl alcohol units, and not by way of linearly polymerizing monomers.For example, vinyl acetate monomers once incorporated into the backboneare hydrolyzed to form vinyl alcohol units. For the purposes of thepresent invention, linear polymer units may be directly introduced, i.e.via linearly polymerizing units, or indirectly, i.e. via a precursor asin the case of vinyl alcohol cited herein above.

Each R¹ is independently hydrogen, C₁-C₄ alkyl, substituted orunsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic,heterocyclic, and mixtures thereof. Preferably R¹ is hydrogen, C₁-C₄alkyl, phenyl, and mixtures thereof, more preferably hydrogen andmethyl.

Each R² is independently hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy,substituted or unsubstituted phenyl, substituted or unsubstitutedbenzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferred R² ishydrogen, C₁-C₄ alkyl, and mixtures thereof. Each Z is independentlyhydrogen; hydroxyl; halogen; —(CH₂)_(m)R, wherein R is hydrogen,hydroxyl, halogen, nitrilo, —OR³, —O(CH₂)_(n)N(R³)₂,—O(CH₂)_(n)N⁺(R³)₃X⁻, —OCO(CH₂)_(n)N(R³)₂, —OCO(CH₂)_(n)N⁺(R³)₃X⁻,—NHCO(CH₂)_(n)N(R³)₂, —NHCO(CH₂)_(n)N⁺(R³)₃X⁻, —(CH₂)_(n)N(R³)₂,—(CH₂)_(n)N⁺(R³)₃X⁻, a non-aromatic nitrogen heterocycle comprising aquaternary ammonium ion, a non-aromatic nitrogen heterocycle comprisingan N-oxide moiety, an aromatic nitrogen containing heterocyclic whereinone or more or the nitrogen atoms is quaternized; an aromatic nitrogencontaining heterocycle wherein at least one nitrogen is an N-oxide;—NHCHO (formamide), or mixtures thereof; wherein each R³ isindependently hydrogen, C₁-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixturesthereof; X is a water soluble anion; the index n is from 0 to 6;carbocyclic, heterocyclic, or mixtures thereof; —(CH₂)_(m)COR′ whereinR′ is —OR³, —O(CH₂)_(n)N(R³)₂, —O(CH₂)_(n)N⁺(R³)₃X⁻,—NR³(CH₂)_(n)N(R³)₂, —NR³(CH₂)_(n)N⁺(R³)₃X⁻, —(CH₂)_(n)N(R³)₂,—(CH₂)_(n)N⁺(R³)₃X⁻, or mixtures thereof, wherein R³, X, and n are thesame as defined herein above. A preferred Z is —O(CH₂)_(n)N⁺(R³)₃X⁻,wherein the index n is 2 to 4. The index m is from 0 to 6, preferably 0to 2, more preferably 0.

Non-limiting examples of linearly polymerizing monomers comprising aheterocyclic Z unit includes 1-vinyl-2-pyrrolidinone, 1-vinylimidazole,2-vinyl-1,3-dioxolane, 4-vinyl-1-cyclohexene1,2-epoxide, and2-vinylpyridine.

The polymers and co-polymers of the present invention comprise Z unitswhich have a cationic charge or which result in a unit which forms acationic charge in situ. When the co-polymers of the present inventioncomprise more than one Z unit, for example, Z¹, Z², . . . Z^(n) units,at least about 1% of the monomers which comprise the co-polymers willcomprise a cationic unit. Preferred cationic units include—O(CH₂)_(n)N⁺(R³)₃X⁻ and —(CH₂)_(n)N⁺(R³)₃X⁻. When the co-polymers ofthe present invention are formed from two monomers, Z¹ and Z², the ratioof Z¹ to Z² is preferably from about 9:1 to about 1:9.

A non-limiting example of a Z unit which can be made to form a cationiccharge in situ is the —NHCHO unit, formamide. The formulator can preparea polymer or co-polymer comprising formamide units some of which aresubsequently hydrolyzed to form vinyl amine equivalents. For example theformulator may prepare a co-polymer having the general formula:

which comprises a formamide unit and then subsequently treat theco-polymer such that some of the formamide units are hydrolyzed to forma co-polymer comprising vinyl amine units, said polymer having theformula:

wherein Z may be a cationic unit comprising or non-cationic unitcomprising moiety and x′+x″=x.

Another class of preferred linearly polymerizable monomers comprisecationically charged heteroaromatic Z units having the formula:

an non-limiting example of which is 4-vinyl (N-alkyl)pyridine wherein R¹and R² are each hydrogen and R⁶ is methyl.

Another class of preferred linearly polymerizable monomers whichcomprises a heterocyclic ring includes Z units comprising an N-oxide,for example, the N-oxide having the formula:

a non-limiting example of which is 4-vinyl pyridine N-oxide.

N-alkyl vinylpyridine monomers and N-oxide vinylpyridine monomers can besuitably combined with other non aromatic monomers, inter alia, vinylamine. However, preferred polymers of the present invention includecopolymers derived from a combination of quaternized, N-oxide, andnitrogen containing heteroaromatic monomers, non-limiting examples ofwhich includes a copolymer of N-methyl vinyl pyridine and vinyl pyridinein a ratio of 4:1; a copolymer of N-methyl vinyl pyridine and vinylpyridine in a ratio of 4:6; a co-polymer of poly(N-methyl vinylpyridine) and vinyl pyridine N-oxide in a ratio of polymer to monomer of4:1; poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratioof polymer to monomer of 4:6; and mixtures thereof.

A preferred linear co-polymer according to the present has the formula:

wherein Z¹ has the formula:

Z² has the formula:

wherein X is chlorine; x has the value of from about 10 to about100,000; y has the value of from about 10 to about 100,000; the ratio ofx to y is from 9:1 to 1:9. Co-polymers of this type are available as,e.g., Sedipur® CF104 ex BASF. As described herein above, some preferredpolymer residues may be formed by treatment of the resulting polymer.For example, vinyl amine residues are preferably introduced viaformamide monomers which are subsequently hydrolyzed to the free aminounit. Also vinyl alcohol units are obtained by hydrolysis of residuesformed form vinyl acetate monomers. Likewise, acrylic acid residues maybe esterified after polymerization, for example, units having theformula:

may be more conveniently formed after the backbone has been formed bypolymerization with acrylic acid or acrylic acid precursor monomers.

II) Cyclic Units Derived from Cyclically Polymerizing Monomers

The polymers or co-polymers of the present invention can comprise one ormore cyclic polymer units which are derived from cyclically polymerizingmonomers. Cyclically polymerizing monomers are defined herein asmonomers which under standard polymerizing conditions result in a cyclicpolymer residue as well as serving to linearly propagate polymerization.Preferred cyclically polymerizing monomers of the present invention havethe formula:

wherein each R⁴ is independently an olefin comprising unit which iscapable of propagating polymerization in addition to forming a cyclicresidue with an adjacent R⁴ unit; R⁵ is C₁-C₁₂ linear or branched alkyl,benzyl, substituted benzyl, and mixtures thereof; X is a water solubleanion.

Non-limiting examples of R⁴ units include allyl and alkyl substitutedallyl units. Preferably the resulting cyclic residue is a six-memberring comprising a quaternary nitrogen atom.

R⁵ is preferably C₁-C₄ alkyl, preferably methyl.

An example of a cyclically polymerizing monomer is dimethyl diallylammonium having the formula:

which results in a polymer or co-polymer having units with the formula:

wherein preferably the index z is from about 10 to about 50,000.

III) Mixtures Thereof

The polymers or co-polymers of the present invention must retain a netcationic charge, whether the charged is developed in situ, or whetherthe polymer or co-polymer itself has a formal positive charge.Preferably the polymer or co-polymer has at least 10%, more preferablyat least about 25%, more preferably at least about 35%, most preferablyat least about 50% of the residues comprise a cationic charge.

The polymers or co-polymers of the present invention can comprisemixtures of linearly and cyclically polymerizing monomers, for examplethe poly(dimethyldiallyl-ammonium chloride/acrylamide) co-polymer havingthe formula:

wherein Z¹, Z², x, y, and z are the same as defined herein above and Xis chloride ion.

A particularly preferred embodiment of this invention is the compositioncomprising a polymer based on dimethyldiallylammonium chloride and acopolymer which is based upon acrylamide with a co-monomer selected fromthe group consisting of N,N dialkylaminoalkyl(meth)acrylate, N,Ndialkylaminoalkylacrylate, N,N dialkylaminoalkylacrylamide, N,Ndialkylaminoalkyl(meth)acrylamide, their quaternized derivatives andmixtures thereof.

Non-limiting examples of preferred polymers according to the presentinvention include dye maintenance copolymers comprising:

i) a first monomer selected from the group consisting of N,Ndialkylaminoalkyl(meth)acrylate, N,N dialkylaminoalkylacrylate, N,Ndialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide,their quaternized derivatives and mixtures thereof; and

ii) a second monomer selected from the group consisting of acrylic acid,methacrylic acid, C₁-C₆ alkylmethacrylate, C₁-C₆ alkyl acrylate, C₁-C₈hydroxyalkylacrylate, C₁-C₈ hydroxyalkylmethacrylate, acrylamide, C₁-C₁₆alkyl acrylamide, C₁-C₁₆ dialkylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid or its alkali salt, methacrylamide, C₁-C₁₆alkylmethacrylamide, C₁-C₁₆ dialkylmethacrylamide, vinyl formamide,vinylacetamide, vinyl alcohol, C₁-C₈ vinylalkylether, vinyl pyridine,itaconic acid, vinyl acetate, vinyl propionate, vinyl butyrate andmixtures thereof;

wherein the copolymer comprises at least 25 mole % of the first monomer.

Adjunct Ingredients

The compositions of the present invention may also optionally compriseone or more adjunct ingredients. Non-limiting examples of adjunctingredients are selected from the group consisting of detersivesurfactants, electrolytes, stabilizers, low molecular weight watersoluble solvents, chelating agents, dispersibility aids, soil releaseagents, nonionic fabric softening agents, concentration aid, perfume,preservatives, colorants, optical brighteners, opacifiers, germicides,fungicides, anti-corrosion agents, antifoam agents, and mixturesthereof.

The following are applications which describe various detergentadditive, methods of making these additives and methods of using themare all included herein by reference. WO 99/07813 A1 Randall et al.,“Laundry Detergent Compositions with Amino Acid Based Polymers toProvide Appearance and Integrity Benefits to Fabrics LaunderedTherewith”; WO 99/07814 A1 Randall et al., “Laundry DetergentCompositions with Amino Acid Based Polymers to Provide Appearance andIntegrity Benefits to Fabrics Laudered Therewith”; WO 99/14299 A1Panandiker et al., “Laundry Detergent Compositions with AnionicallyModified, Cyclic Amine Based Polymers; WO 99/14300 A1 Panandiker et al.,“Laundry Detergent Compositions with Cyclic Amine-Based Polymers toProvide Appearance and Integrity Benefits to Fabrics LaunderedTherewith”; WO 99/14301 A1 Panandiker et al., “Laundry DetergentCompositions and Fabric Conditioning Compositions with Oxidized CyclicAmine-Based Polymers”; and U.S. 99/23146 Panandiker et al., “LaundryDetergent Compositions with A Combination of Cyclic Amine Based Polymersand Hydrophobically Modified Carboxy Methyl Cellulose”.

Surfactant System

The laundry detergent compositions of the present invention comprise asurfactant system. The surfactant systems of the present invention maycomprise any type of detersive surfactant, non-limiting examples ofwhich include one or more mid-chain branched alkyl sulfate surfactants,one or more mid-chain branched alkyl alkoxy sulfate surfactants, one ormore mid-chain branched aryl sulfonate surfactants, one or more nonmid-chain branched sulphonates, sulphates, cationic surfactants,zwitterionic surfactants, ampholytic surfactants, and mixtures thereof.

The total amount of surfactant present in the compositions of thepresent invention is from about 4% by weight, preferably from about 10%more preferably from about 15% to about 60%, preferably to about 30% byweight, of said composition.

Nonlimiting examples of surfactants useful herein include:

a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);

b) C₆-C₁₈ mid-chain branched aryl sulfonates (BLAS);

c) C₁₀-C₂₀ primary, α or ω-branched, and random alkyl sulfates (AS);

d) C₁₄-C₂₀ mid-chain branched alkyl sulfates (BAS);

e) C₁₀-C₁₈ secondary (2,3) alkyl sulfates as described in U.S. Pat. No.3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041 Lutz,issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al., issued Sep.20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued Feb. 14, 1995 eachincorporated herein by reference;

f) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably x is from1-7;

g) C₁₄-C₂₀ mid-chain branched alkyl alkoxy sulfates (BAE_(x)S);

h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5 ethoxyunits;

i) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates whereinthe alkoxylate units are a mixture of ethyleneoxy and propyleneoxyunits, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers inter alia Pluronic® ex BASF whichare disclosed in U.S. Pat. No. 3,929,678 Laughlin et al., issued Dec.30, 1975, incorporated herein by reference;

j) C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x);

k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647 Llenado,issued Jan. 26, 1986, incorporated herein by reference;

l) Polyhydroxy fatty acid amides having the formula:

wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the group consisting ofhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, Q is a polyhydroxyalkylmoiety having a linear alkyl chain with at least 3 hydroxyls directlyconnected to the chain, or an alkoxylated derivative thereof; preferredalkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q isderived from a reducing sugar in a reductive amination reaction, morepreferably Q is a glycityl moiety; Q is more preferably selected fromthe group consisting of —CH₂(CHOH)_(n)CH₂OH,—CH(CH₂OH)(CHOH)_(n-1)CH₂OH, —CH₂(CHOH)₂(CHOR′)(CHOH)CH₂OH, andalkoxylated derivatives thereof, wherein n is an integer from 3 to 5,inclusive, and R′ is hydrogen or a cyclic or aliphatic monosaccharide,which are described in U.S. Pat. No. 5,489,393 Connor et al., issuedFeb. 6, 1996; and U.S. Pat. No. 5,45,982 Murch et al., issued Oct. 3,1995, both incorporated herein by reference.

A non-limiting example of a nonionic surfactant suitable for use in thepresent invention has the formula:

wherein R is C₇-C₂₁ linear alkyl, C₇-C₂₁ branched alkyl, C₇-C₂₁ linearalkenyl, C₇-C₂₁ branched alkenyl, and mixtures thereof.

R¹ is ethylene; R² is C₃-C₄ linear alkyl, C₃-C₄ branched alkyl, andmixtures thereof; preferably R² is 1,2-propylene. Nonionic surfactantswhich comprise a mixture of R¹ and R² units preferably comprise fromabout 4 to about 12 ethylene units in combination with from about 1 toabout 4 1,2-propylene units. The units may be alternating, or groupedtogether in any combination suitable to the formulator. Preferably theratio of R¹ units to R² units is from about 4:1 to about 8:1. Preferablyan R² units (i.e. 1,2-propylene) is attached to the nitrogen atomfollowed by the balance of the chain comprising from 4 to 8 ethyleneunits.

R² is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl, and mixturesthereof; preferably hydrogen or methyl, more preferably hydrogen.

R⁴ is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl, and mixturesthereof; preferably hydrogen. When the index m is equal to 2 the index nmust be equal to 0 and the R⁴ unit is absent and is instead replaced bya —[(R¹O)_(x)(R²O)_(y)R³] unit.

The index m is 1 or 2, the index n is 0 or 1, provided that when m isequal to 1, n is equal to 1; and when m is 2 n is 0; preferably m isequal to 1 and n is equal to one, resulting in one—[(R¹O)_(x)(R²O)_(y)R³] unit and R⁴ being present on the nitrogen. Theindex x is from 0 to about 50, preferably from about 3 to about 25, morepreferably from about 3 to about 10. The index y is from 0 to about 10,preferably 0, however when the index y is not equal to 0, y is from 1 toabout 4. Preferably all of the alkyleneoxy units are ethyleneoxy units.Those skilled in the art of ethoxylated polyoxyalkylene alkyl amidesurface active agents will recognized that the values for the indices xand y are average values and the true values may range over severalvalues depending upon the process used to alkoxylate the amides.

The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula:

the alkyl alkoxy sulfates have the formula:

the alkyl alkoxylates have the formula:

wherein R, R¹, and R² are each independently hydrogen, C₁-C₃ alkyl, andmixtures thereof; provided at least one of R, R¹, and R² is nothydrogen; preferably R, R¹, and R² are methyl; preferably one of R, R¹,and R² is methyl and the other units are hydrogen. The total number ofcarbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants is from 14 to 20; the index w is an integer from 0to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z isan integer of at least 1; provided w+x+y+z is from 8 to 14 and the totalnumber of carbon atoms in a surfactant is from 14 to 20; R³ is C₁-C₄linear or branched alkylene, preferably ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.However, a preferred embodiment of the present invention comprises from1 to 3 units wherein R³ is 1,2-propylene, 1,3-propylene, or mixturesthereof followed by the balance of the R³ units comprising ethyleneunits. Another preferred embodiment comprises R³ units which arerandomly ethylene and 1,2-propylene units. The average value of theindex m is at least about 0.01. When the index m has low values, thesurfactant system comprises mostly alkyl sulfates with a small amount ofalkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may bepresent in the alkyl chain, however, this embodiment is not desired.

M denotes a cation, preferably hydrogen, a water soluble cation, andmixtures thereof. Non-limiting examples of water soluble cations includesodium, potassium, lithium, ammonium, alkyl ammonium, and mixturesthereof.

Detergent Builder

The detergent compositions herein may also comprise from about 0.1% to80% by weight of a detergent builder. Preferably such compositions inliquid form will comprise from about 1% to 10% by weight of the buildercomponent. Preferably such compositions in granular form will comprisefrom about 1% to 50% by weight of the builder component. Detergentbuilders are well known in the art and can comprise, for example,phosphate salts as well as various organic and inorganic nonphosphorusbuilders.

Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxy sulfonates. Suitablepolycarboxylates for use herein are the polyacetal carboxylatesdescribed in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 toCrutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 toCrutchfield et al., both of which are incorporated herein by reference.Particularly preferred polycarboxylate builders are the oxydisuccinatesand the ether carboxylate builder compositions comprising a combinationof tartrate monosuccinate and tartrate disuccinate described in U.S.Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure ofwhich is incorporated herein by reference.

Examples of suitable nonphosphorus, inorganic builders include thesilicates, aluminosilicates, borates and carbonates. Particularlypreferred are sodium and potassium carbonate, bicarbonate,sesquicarbonate, tetraborate decahydrate, and silicates having a weightratio of SiO₂ to alkali metal oxide of from about 0.5 to about 4.0,preferably from about 1.0 to about 2.4. Also preferred arealuminosilicates including zeolites. Such materials and their use asdetergent builders are more fully discussed in Corkill et al., U.S. Pat.No. 4,605,509, the disclosure of which is incorporated herein byreference. Also discussed in U.S. Pat. No. 4,605,509 are crystallinelayered silicates which are suitable for use in the detergentcompositions of this invention.

Optional Detergent Ingredients

In addition to the surfactants, builders and dye maintenance polymers ofthe detergent compositions of the present invention can also include anynumber of additional optional ingredients. These include conventionaldetergent composition components such as enzymes and enzyme stabilizingagents, suds boosters or suds suppressers, anti-tarnish andanticorrosion agents, bleaching agents, soil suspending agents, soilrelease agents, germicides, pH adjusting agents, non-builder alkalinitysources, chelating agents, organic and inorganic fillers, solvents,hydrotropes, optical brighteners, dyes and perfumes.

pH adjusting agents may be necessary in certain applications where thepH of the wash solution is greater than about 10.0 because the fabricintegrity benefits of the defined compositions begin to diminish at ahigher pH. Hence, if the wash solution is greater than about 10.0 afterthe addition of the dye maintenance polymers of the present invention apH adjuster should be used to reduce the pH of the washing solution tobelow about 10.0, preferably to a pH of below about 9.5 and mostpreferably below about 7.5. Suitable pH adjusters will be known to thoseskilled in the art.

A preferred optional ingredients for incorporation into the detergentcompositions herein comprises a bleaching agent, e.g., a peroxygenbleach. Such peroxygen bleaching agents may be organic or inorganic innature. Inorganic peroxygen bleaching agents are frequently utilized incombination with a bleach activator.

Useful organic peroxygen bleaching agents include percarboxylic acidbleaching agents and salts thereof. Suitable examples of this class ofagents include magnesium monoperoxyphthalate hexahydrate, the magnesiumsalt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acidand diperoxydodecanedioic acid. Such bleaching agents are disclosed inU.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European PatentApplication EP-A-133,354, Banks et al., Published Feb. 20, 1985; andU.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6,1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used, generally inparticulate form, in the detergent compositions herein. Inorganicbleaching agents are in fact preferred. Such inorganic peroxygencompounds include alkali metal perborate and percarbonate materials. Forexample, sodium perborate (e.g. mono- or tetra-hydrate) can be used.Suitable inorganic bleaching agents can also include sodium or potassiumcarbonate peroxyhydrate and equivalent “percarbonate” bleaches, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) canalso be used. Frequently inorganic peroxygen bleaches will be coatedwith silicate, borate, sulfate or water-soluble surfactants. Forexample, coated percarbonate particles are available from variouscommercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaching agents, e.g., the perborates, thepercarbonate, etc., are preferably combined with bleach activators,which lead to the in situ production in aqueous solution (i.e., duringuse of the compositions herein for fabric laundering/bleaching) of theperoxy acid corresponding to the bleach activator. Various non-limitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, IssuedApr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1,1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) andtetraacetyl ethylene diamine (TAED) activators are typical andpreferred. Mixtures thereof can also be used. See also the hereinbeforereferenced U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Other useful amido-derived bleach activators are those of the formulae:

R¹N(R⁵)C(O)R²C(O)L

or

R¹C(O)N(R⁵)R²C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms. R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene-sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate andmixtures thereof as described in the hereinbefore referenced U.S. Pat.No. 4,634,551.

Another class of useful bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al. in U.S. Pat. No. 4,966,723, IssuedOct. 30, 1990, incorporated herein by reference. See also U.S. Pat. No.4,545,784, Issued to Sanderson, Oct. 8, 1985, incorporated herein byreference, which discloses acyl caprolactams, including benzoylcaprolactam, adsorbed into sodium perborate.

If utilized, peroxygen bleaching agent will generally comprise fromabout 2% to 30% by weight of the detergent compositions herein. Morepreferably, peroxygen bleaching agent will comprise from about 2% to 20%by weight of the compositions. Most preferably, peroxygen bleachingagent will be present to the extent of from about 3% to 15% by weight ofthe compositions herein. If utilized, bleach activators can comprisefrom about 2% to 10% by weight of the detergent compositions herein.Frequently, activators are employed such that the molar ratio ofbleaching agent to activator ranges from about 1:1 to 10:1, morepreferably from about 1.5:1 to 5:1.

Additional suitable bleaching agents and bleach activators are disclosedin one or more of the co-pending PCT Applications listed in Table A andincorporated herein by reference.

Another highly preferred optional ingredient in the detergentcompositions herein is a detersive enzyme component. Enzymes can beincluded in the present detergent compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, cellulases, peroxidases,and mixtures thereof of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin. Preferred selections are influencedby factors such as pH-activity and/or stability, optimalthermostability, and stability to active detergents, builders and thelike. In this respect bacterial or fungal enzymes are preferred, such asbacterial amylases and proteases, and fungal cellulases.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry detergentcomposition. Preferred enzymes for laundry purposes include, but are notlimited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levelssufficient to provide a “cleaning-effective amount”. The term“cleaning-effective amount” refers to any amount capable of producing acleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as fabrics. In practicalterms for current commercial preparations, typical amounts are up toabout 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzymeper gram of the detergent composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition. Higher active levels may be desirablein highly concentrated detergent formulations.

Cellulases usable herein include those disclosed in U.S. Pat. No.4,435,307, Barbesgoard et al., Mar. 6, 1984, and GB-A-2.075.028;GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) areespecially useful. See also WO 9117243 to Novo.

The enzyme-containing compositions herein may optionally also comprisefrom about 0.001% to about 10%, preferably from about 0.005% to about8%, most preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

Detergent Composition Preparation

The detergent compositions according to the present invention can be inliquid, paste or granular form. Such compositions can be prepared bycombining the essential and optional components in the requisiteconcentrations in any suitable order and by any conventional means. Theforgoing description of uses for the dye maintenance polymers definedherein are intended to be exemplary and other uses will be apparent tothose skilled in the art and are intended to be within the scope of thepresent invention.

Granular compositions, for example, are generally made by combining basegranule ingredients, e.g., surfactants, builders, water, etc., as aslurry, and spray drying the resulting slurry to a low level of residualmoisture (5-12%). The remaining dry ingredients, e.g., granules of theessential dye maintenance polymers, can be admixed in granular powderform with the spray dried granules in a rotary mixing drum. The liquidingredients, e.g., solutions of the essential dye maintenance polymers,enzymes, binders and perfumes, can be sprayed onto the resultinggranules to form the finished detergent composition. Granularcompositions according to the present invention can also be in “compactform”, i.e. they may have a relatively higher density than conventionalgranular detergents, i.e. from 550 to 950 g/l. In such case, thegranular detergent compositions according to the present invention willcontain a lower amount of “inorganic filler salt”, compared toconventional granular detergents; typical filler salts are alkalineearth metal salts of sulphates and chlorides, typically sodium sulphate;“compact” detergents typically comprise not more than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in“compact form”, in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents. Addition of the dyemaintenance polymers to liquid detergent or other aqueous compositionsof this invention may be accomplished by simply mixing into the liquidsolutions the desired dye maintenance polymers.

Fabric Laundering Method

The present invention also provides a method for laundering fabrics in amanner which imparts fabric appearance benefits provided by the dyemaintenance polymers used herein. Such a method employs contacting thesefabrics with an aqueous washing solution formed from an effective amountof the detergent compositions hereinbefore described or formed from theindividual components of such compositions. Contacting of fabrics withwashing solution will generally occur under conditions of agitationalthough the compositions of the present invention may also be used toform aqueous unagitated soaking solutions for fabric cleaning andtreatment. As discussed above, it is preferred that the washing solutionhave a pH of less than about 10.0, preferably it has a pH of about 9.5and most preferably it has a pH of about 7.5.

Agitation is preferably provided in a washing machine for good cleaning.Washing is preferably followed by drying the wet fabric in aconventional clothes dryer. An effective amount of a high density liquidor granular detergent composition in the aqueous wash solution in thewashing machine is preferably from about 500 to about 7000 ppm, morepreferably from about 1000 to about 3000 ppm.

EXAMPLES

The following examples illustrate the compositions and methods of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention.

Example I

TABLE I comprises numerous examples according to the present inventionalong with some comparative examples of material known to the art oflaundry detergents. The chemical structures shown in the examples beloware idealized structures. Side reactions expected to occur during thecondensation are not shown.

TABLE II Ex. # Material 1 Poly(N,N dimethylaminoethyl methacrylate) 2Poly(N,N dimethylaminoethyl methacrylate), MW 9700 3 Poly(N,Ndimethylaminoethyl methacrylate), MW 15,700 4 Poly(N,Ndimethylaminoethyl methacrylate), MW 39,700 5 Poly(N,Ndimethylaminoethyl methacrylate-co- dimethylacrylamide) ratio 1:1 MW13670 6 Poly(N,N dimethylaminoethyl methacrylate-co- dimethylacrylamide)ratio 2:1, MW 14,400 7 Poly(N,N dimethylaminoethyl methacrylate-co-dimethylacrylamide) ratio 3:1 MW 16,300 8 Methyl quat of poly(N,Ndimethylaminoethyl methacrylate) 9 Amine oxide of Poly(N,Ndimethylaminoethyl methacrylate) 10 Poly(N,Ndimethylaminoethylmethacrylate-co-octylacrylamide) ratio 3:1, MW = 673011 Poly(N,N dimethylaminoethyl methacrylate-co-acrylic acid) ratio 1:1,MW = 14,950 12 Poly(N,N dimethylaminoethyl methacrylate-acrylamide)ratio 1:1, Poly(N,N dimethylaminoethyl methacrylate-propane sultone)ratio 1:1, 13 Poly(dimethyldiallylammonium chloride) sold under thetrade name Merquat 100 by Calgon Corporation, Pittsburg, PA. 14Poly(dimethyldiallylammonium chloride-co-acrylamide) sold under thetrade name Merquat Plus (Calgon Corporation, Pittsburg, PA). 15Poly(dimethyldiallylammonium chloride-co-acrylamide) sold under thetrade name Merquat 550 (Calgon Corporation, Pittsburg, PA). 16Poly(dimethyldiallylammonium chloride-co-acrylic acid) sold under thetrade name Merquat 280 (Calgon Corporation, Pittsburg, PA). 17 Poly(Nmethyl,N octadecyl aminoethyl methacrylate) quaternized with dimethylsulfate (CTFA nomenclature polyquaternium 8) 18 Ionene polymer ofN,N,N′,N′ tetramethyl hexanediamine and 1,6 dibromohexane in the ratio4:3 19 Polyvinylamine 20 Poly(vinylamine-co-vinylalcohol) ratio 1:1 21Poly(vinylamine-co-acrylic acid) ratio 1:1 22 Polyallylamine 23poly(vinylamine-co-vinyl formamide) ratio 1:1 24 polyvinylamineethoxylated with 0.5 moles of ethylene oxide per N—H 25 polyvinylaminepropoxylated with 0.5 moles of propylene oxide per N—H 26 Polyquaternium2 (CTFA nomenclature) sold under the trade name Mirapol A15 by RhonePoulenc, Paris, France. 27 Polyquaternium 17 (CTFA nomenclature) soldunder the trade name Mirapol AD-1 by Rhone Poulenc, Paris, France. 28Copolymer of N methylvinyl pyridine co-vinyl pyridine (ratio 4:1) 29Copolymer of N methylvinyl pyridine co-vinyl pyridine (ratio 4:6) 30Poly(N methylvinyl pyridine co-vinyl pyridine N oxide) ratio 4:1 31Poly(N methylvinyl pyridine co-vinyl pyridine N oxide) ratio 4:6

Example II

Granular Detergent Test Composition Preparation

Several heavy duty granular detergent compositions are preparedcontaining one or more dye maintenance polymer having a DMP according tothis invention. These granular detergent compositions all have thefollowing basic formula:

TABLE II Component Wt. % C₁₂ Linear alkyl benzene sulfonate  9.31 C₁₄₋₁₅alkyl ether (0.35 EO) sulfate  12.74 Zeolite Builder  27.79 SodiumCarbonate  27.31 PEG 4000  1.60 Dispersant  2.26 C₁₂₋₁₃ AlcoholEtholylate (9 EO)  1.5 Sodium Perborate  1.03 Soil Release Polymer  0.41Enzymes  0.59 Dye Maintenance Polymer  3.0 Perfume, Brightener, SudsSuppressor, Other Balance Minors, Moisture, Sulfate 100%

Example III

Liquid Detergent Test Composition Preparation

Several heavy duty liquid detergent compositions are prepared containingone or more dye maintenance polymer having a DMP according to thisinvention. These liquid detergent compositions all have the followingbasic formula:

TABLE III Component Wt. % C₁₂₋₁₅ alkyl ether (2.5) sulfate  38 C₁₂glucose amide  6.86 Citric Acid  4.75 C₁₂₋₁₄ Fatty Acid  2.00 Enzymes 1.02 MEA  1.0 Propanediol  0.36 Borax  6.58 Dispersant  1.48 Na TolueneSulfonate  6.25 Dye Maintenance Polymer  1.0 Dye, Perfume, Brighteners,Preservatives, Suds Balance Suppressor, Other Minors, Water 100%

Example IV

Granular Detergent Test Composition Preparation

Several granular detergent compositions are prepared containing one ormore dye maintenance polymer having a DMP according to this invention.Such granular detergent compositions all have the following basicformula:

TABLE IV Example Comparative Component Wt. % Wt. % Na C₁₂ Linear alkylbenzene sulfonate  9.40  9.40 Na C₁₄₋₁₅ alkyl sulfonate  11.26  11.26Zeolite Builder  27.79  27.79 Sodium Carbonate  27.31  27.31 PEG 4000 1.60  1.60 Dispersant, Na polyacrylate  2.26  2.26 C₁₂₋₁₃ alkyletholylate (E9)  1.5  1.5 Sodium Perborate  1.03  1.03 Dye MaintenancePolymer  0.8  0 Other Adjunct ingredients Balance Balance 100% 100%

What is claimed is:
 1. A detergent compositions comprising: a) fromabout 4% to about 70% by weight, of a surfactant; b) from about 0.01% toabout 10% by weight, of a dye maintenance co-polymer, said copolymerhaving the general formula:

 x has the value of from about 10 to about 100,000; y has the value offrom about 10 to about 100,000; the ratio of x to y is from 9:1 to 1:9;each Z is independently a heterocycling ring containing an N-oxide, acationically charged heteroaromatic monomer, a cyclically polymerizingmonomer, or (CH₂)_(m)COR′, wherein R′ is selected from: i) —OR³; ii)—O(CH₂)_(n)N(R³)₂; iii) —O(CH₂)_(n)N⁺(R³)₃X⁻; iv) —NR³(CH₂)_(n)N(R³)₂;v) —NR³(CH₂)_(n)N⁺(R³)₃X⁻; vi) —(CH₂)_(n)N(R³)₂; vii)—(CH₂)_(n)N⁺(R³)₃X⁻; viii) or mixtures thereof; each R³ is independentlyhydrogen, C₁-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is awater soluble anion; the index n is from 0 to 6; the index m is from 0to 6; provided said polymer or co-polymer has a net cationic charge; andwherein said dye maintenance polymer is not an polyethyleneimine oralkoxylated derivative thereof; and c) the balance carriers and otheradjunct ingredients.
 2. A composition according to claim 1 comprisingfrom about 0.1% to about 7% by weight of said dye maintenance polymer.3. A composition according to claim 1 wherein Z has the formula:


4. A composition according to claim 1 wherein comprises a cyclicallypolymerizing monomer, said cyclically polymerizing monomer having theformula:

wherein R⁵ is C₁-C₄ alkyl, and mixtures thereof; X is a water solubleanion.
 5. A composition according to claim 1 comprising a co-polymerwherein Z has the formula: —(CH₂)_(m)COR′ wherein each R′ isindependently —O(CH₂)_(n)N(R³)₂; —O(CH₂)_(n)N⁺(R³)₃X⁻; —(CH₂)_(n)N(R³)₂;—(CH₂)_(n)N⁺(R³)₃X⁻; and mixtures thereof; m is 0, n is from 2 to
 4. 6.A composition according to claim 1 comprising a co-polymer wherein theco-polymer further comprises vinyl amine units having the formula:

wherein x′+x″=x.
 7. A composition according to claim 1 wherein Zcomprises a cationically charged heteroaromatic monomer, saidcationically charged heteroaromatic monomer having the formula:

wherein R¹ and R² are each hydrogen and R⁶ is methyl.
 8. A compositionaccording to claim 1 wherein Z comprises a heterocyclic ring containingan N-oxide, said heterocyclic ring containing an N-oxide having theformula:

wherein R¹ and R² are each hydrogen.
 9. A composition according to claim1 wherein said adjunct ingredients are selected from the groupconsisting of electrolytes, stabilizers, low molecular weight watersoluble solvents, chelating agents, dispersibility aids, soil releaseagents, nonionic fabric softening agents, concentration aid, perfume,preservatives, colorants, optical brighteners, opacifiers, germicides,fungicides, anti-corrosion agents, antifoam agents, and mixturesthereof.
 10. A method for reducing the loss of fabric dye comprising thesteps of: i) contacting dyed fabric with a laundry detergent comprising:a) from about 4% to about 70% by weight, of a surfactant; b) from about0.01% to about 5% by weight, of a dye maintenance copolymer of claim 1;and c) the balance carriers and other adjunct ingredients; and ii)agitation; and iii) optionally, drying the fabric.